CN104211931B - A kind of pure plant oil based polyenoid class UV-curable prepolymer - Google Patents
A kind of pure plant oil based polyenoid class UV-curable prepolymer Download PDFInfo
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- CN104211931B CN104211931B CN201410393867.8A CN201410393867A CN104211931B CN 104211931 B CN104211931 B CN 104211931B CN 201410393867 A CN201410393867 A CN 201410393867A CN 104211931 B CN104211931 B CN 104211931B
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- oil
- vegetable oil
- pure plant
- curable prepolymer
- undecenoic acid
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Abstract
The invention belongs to field of light-sensitive high molecular materials, disclose the preparation method of pure plant oil based UV-curable prepolymer, comprise the following steps: (1) adopts hydrogen peroxide and formic acid to carry out epoxidation to vegetable oil. (2) in epoxidized vegetable oil, add undecenoic acid open loop epoxide group, under solvent-free existence, within 8 hours, prepare the vegetable oil-based polyols of undecenoic acid modification in 170 DEG C of reactions. (3) the hendecene acyl chlorides being made by undecenoic acid is mixed in ethyl acetate with the vegetable oil-based polyols of undecenoic acid modification, and under ice bath, add triethylamine to react 2 hours, then at room temperature stir 24 hours, sodium hydrate aqueous solution and distilled water washing with 1% respectively after suction filtration, dried over mgso is removed desolventizing and is obtained product. The present invention has alleviated the dependence to petroleum resources; Have branched structure, viscosity is low; The two keys of UV-curable are in end position, reactive high; Containing a large amount of long alkane chains, pliability is good.
Description
Technical field
The present invention relates to field of light-sensitive high molecular materials, particularly renewable resource is in the coating material solidified application of UV.
Background technology
UV curing technology refers under UV effect, and liquid-state oligomers and monomer form the process of solid product through cross-linked polymeric, because of its rapid curing, energy-and time-economizing, wide adaptability, the friendly industrial technology with " 5E " feature that is summarized as of energy economy & environment. UV curing system is mainly made up of acrylic ester prepolymer, monomer diluent and light trigger at present, and its performance is mainly determined by prepolymer. The initiation material of present stage UV curing formula is petroleum chemicals, the in the situation that day by day exhausted and price being continuous soaring at petroleum resources, utilizes renewable resource to have important foundation research and economic implications for the novel UV of development of raw materials is coating material solidified.
Vegetable oil can be regenerated by photosynthesis, growth cycle is short, low price and the macromolecule based on vegetable oil have biodegradation and eco-friendly feature, and therefore vegetable oil is one of oil replacement raw material of tool potentiality. But due to the extremely restriction of derivative kind and architectural feature of utilized renewable resource, cause plant oil based UV to solidify the lower and film performance of few, the renewable carbon content of prepolymer kind and be short of to some extent.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of renewable, source is wide, cost is low and the pure plant oil based prepolymer of UV-curable of easy preparation and preparation method thereof.
In the present invention taking the derivative-undecenoic acid of vegetable oil and castor oil as raw material, can prepare the curing prepolymer of pure plant oil based UV by high productivity by three-step reaction and simple post processing, this plant oil based UV solidifies the synthetic of prepolymer and does not report at present, consumption at preparation process solvent is less, productive rate is high and its cost is low, meets day by day severe environmental regulation requirement.
Pure plant oil based a kind of prepolymer of UV-curable provided by the present invention, its representational structural formula is:
Described vegetable oil is one or more the mixture in the vegetable oil that contains more than 2 or 2 unsaturated double-bond, is preferably one or more mixture of rapeseed oil, corn oil, soybean oil, olive oil, grape-kernel oil, linseed seed oil and tung oil. , adding light trigger or do not adding light trigger; Under the existence of UV light or non-existent condition, can, with multi-thiol material at 20-30 DEG C of rapid curing, obtain highly cross-linked film.
Described pure plant oil based UV-curable prepolymer, its preparation method mainly comprises following three steps: (1) adopts hydrogen peroxide and formic acid to carry out epoxidation to vegetable oil; (2) in epoxidized vegetable oil, add undecenoic acid open loop epoxide group, under solvent-free existence, within 8 hours, prepare the vegetable oil-based polyols of undecenoic acid modification in 170 DEG C of reactions; (3) the hendecene acyl chlorides being made by undecenoic acid is mixed in ethyl acetate with the vegetable oil-based polyols of undecenoic acid modification, and under ice bath, add triethylamine to react 2 hours, then room temperature (20-30 DEG C) stirs 24 hours, after suction filtration, obtains product respectively with removing desolventizing after 1% sodium hydrate aqueous solution and distilled water washing, dried over mgso.
Described pure plant oil based UV-curable prepolymer, the content of its renewable carbon atom is 100%.
Described pure plant oil based UV-curable prepolymer has branched structure, and the degree of branching is relevant to the number of unsaturated double-bond on vegetable oil raw materials, is 1 ~ 2 times of the contained double key number object of vegetable oil.
Described pure plant oil based UV-curable prepolymer, its unsaturated degree of functionality is relevant to the number of unsaturated double-bond on vegetable oil raw materials, is 1 ~ 2 times of the contained double key number object of vegetable oil. On vegetable oil raw materials, the number of unsaturated double-bond is 2 ~ 8.
Described pure plant oil based UV-curable prepolymer, its molecular weight is 1672 ~ 3868g.mol-1。
Described pure plant oil based UV-curable prepolymer, is adding light trigger or is not adding light trigger; UV light exist or non-existent condition under, all can with at room temperature (20-30 DEG C) rapid curing of multi-thiol material, obtain highly cross-linked film.
Described multi-thiol material is the material containing 2 and above sulfydryl, as 1.6-ethanthiol, pentaerythrite tri-thiol propionic ester or pentaerythrite four mercaptopropionic acid esters etc.
Compared with prior art, the present invention has following beneficial effect: the raw materials used vegetable oil of the present invention and undecenoic acid are entirely renewable resource, the content (%BRC) of preparing the renewable carbon of gained prepolymer is 100%, has alleviated the dependence to petroleum resources; Prepare gained prepolymer and have branched structure, the material of ratio of viscosities same molecular amount is low; Prepare the two keys of the contained UV-curable of gained prepolymer in end position, reactive high; Prepare in gained prepolymer and contain a large amount of long alkane chains, can give the pliability that UV solidified coating is good, can be used for the coating material solidified and adhesive of UV.
Brief description of the drawings
Fig. 1 Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure (A: rapeseed oil B: epoxy rapeseed oil C: undecenoic acid open loop epoxy rapeseed oil D: Rap Oil-based prepolymer)
Fig. 2 Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure (A: rapeseed oil B: epoxy rapeseed oil C: undecenoic acid open loop epoxy rapeseed oil D: Rap Oil-based prepolymer).
Detailed description of the invention
The present invention further illustrate main contents of the present invention below in conjunction with specific embodiment, but the present invention is not only confined to following examples in order better to explain.
Embodiment 1
1) get rapeseed oil 5g, 30% hydrogen peroxide 12g and formic acid 5.36g, in flask, are placed in magnetic stirring apparatus and react after 24h under room temperature, add 10ml ethyl acetate, 10ml distilled water, leave standstill 10min layering. Get upper organic phase sodium carbonate liquor washing to alkalescence, with after anhydrous magnesium sulfate drying, suction filtration, revolve and steam except desolventizing, obtain epoxy rapeseed oil;
2) the epoxy rapeseed oil 2.0g making is mixed to (epoxy and carboxyl mol ratio are 1:1) with undecenoic acid 1.47g, react the Rap Oil-based polyalcohol that obtains undecenoic acid modification for 8 hours at 170 DEG C;
3) undecanoyl chlorine 3.2g, triethylamine 1.6g and ethyl acetate 5ml are joined in the Rap Oil-based polyalcohol 3.47g of undecenoic acid modification, under ice bath, react after 2 hours and be warming up to room temperature reaction 24 hours, suction filtration. Liquid phase is respectively with 1% sodium hydrate aqueous solution and distilled water washing, after anhydrous magnesium sulfate drying, suction filtration, revolves steaming, obtains the Rap Oil-based prepolymer (gross production rate is 85%) of UV-curable;
Rap Oil-based UV-curable prepolymer preparation process Raw and intermediate product nucleus magnetic hydrogen spectrum figure are shown in Fig. 1, Fig. 2. The content (%BRC) of preparing the renewable carbon of gained prepolymer is 100%, has alleviated the dependence to petroleum resources; Prepare gained prepolymer and have branched structure, the material of ratio of viscosities same molecular amount is low; Prepare the two keys of the contained UV-curable of gained prepolymer in end position, reactive high; Prepare in gained prepolymer and contain a large amount of long alkane chains, can give the pliability that UV solidified coating is good, can be used for the coating material solidified and adhesive of UV.
Embodiment 2
1) get corn oil 5g, 30% hydrogen peroxide 12g and formic acid 5.36g, in flask, are placed in magnetic stirring apparatus and react 24h, add 10ml ethyl acetate, 10ml to remove distilled water, leave standstill 10min layering. Get upper organic phase sodium carbonate liquor washing to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve and steam except desolventizing, obtain epoxy corn oil;
2) the epoxy corn oil 2.0g obtaining is above mixed to (epoxy and carboxyl mol ratio are 1:1) with undecenoic acid 1.5g, react the corn oil polylol that obtains undecenoic acid modification for 8 hours at 170 DEG C;
3) undecanoyl chlorine 3.6g, triethylamine 1.8g and ethyl acetate 5ml are joined in the Rap Oil-based polyalcohol 3.5g of undecenoic acid modification, under ice bath, react 2 hours, be warming up to room temperature reaction 24 hours, suction filtration, liquid phase is washed with 1% sodium hydrate aqueous solution and distilled water respectively, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain the corn oil based prepolymers (gross production rate is 83%) of UV-curable.
Embodiment 3
1) get olive oil 5g, 30% hydrogen peroxide 8.4g and formic acid 3.75g, in flask, are placed in magnetic stirring apparatus and react 24h, add 10ml ethyl acetate, 10ml distilled water, leave standstill 10min layering. Get upper organic phase sodium carbonate liquor washing to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain epoxy olive oil;
2) the epoxy olive oil 2.0g obtaining is above mixed to (epoxy and carboxyl mol ratio are 1:1) with undecenoic acid 1.1g, react the olive oil polylol that obtains undecenoic acid modification for 8 hours at 170 DEG C;
3) undecanoyl chlorine 2.4g, triethylamine 1.2g and ethyl acetate 5ml are added in the olive oil polylol 3.1g of undecenoic acid modification, under ice bath, react 2 hours, be warming up to room temperature reaction 24 hours, suction filtration. Liquid phase is respectively with 1% sodium hydrate aqueous solution and distilled water washing, after anhydrous magnesium sulfate drying, suction filtration, revolves steaming, obtains the olive oil based prepolymers (gross production rate is 88%) of UV-curable.
Embodiment 4
1) get linseed oil 5g, 30% hydrogen peroxide 18g and formic acid 8g, in flask, are placed in magnetic stirring apparatus and react 24h, add 15ml ethyl acetate, 15ml distilled water, leave standstill 10min layering. Get upper organic phase sodium carbonate liquor washing to alkalescence, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain epoxy linseed oil;
2) the epoxy linseed oil 2.0g obtaining is above mixed to (taking epoxide number and undecenoic acid mol ratio as 1:1) with undecenoic acid 2.2g, react the linseed oil polylol of undecenoic acid modification in 8 hours at 170 DEG C;
3) undecanoyl chlorine 4.8g, triethylamine 2.4g and ethyl acetate 10ml are joined in the linseed oil polylol 4.2g of undecenoic acid modification, under ice bath, react 2 hours, be warming up to room temperature reaction 24 hours, suction filtration. Get liquid phase respectively with 1% sodium hydrate aqueous solution and distilled water washing, after anhydrous magnesium sulfate drying, suction filtration, revolve steaming, obtain the linseed oil based prepolymers (gross production rate is 81%) of UV-curable.
Claims (9)
1. a pure plant oil based polyenoid class UV-curable prepolymer, is characterized in that: adding light trigger or do not adding light trigger; Under the existence of UV light or non-existent condition, can, with multi-thiol material at 20-30 DEG C of rapid curing, obtain highly cross-linked film; Described vegetable oil is one or more the mixture in the vegetable oil that contains more than 2 or 2 unsaturated double-bond;
Its preparation method mainly comprises following three steps: (1) adopts hydrogen peroxide and formic acid to carry out epoxidation to vegetable oil; (2) in epoxidized vegetable oil, add undecenoic acid open loop epoxide group, under solvent-free existence, within 8 hours, prepare the vegetable oil-based polyols of undecenoic acid modification in 170 DEG C of reactions; (3) the hendecene acyl chlorides being made by undecenoic acid is mixed in ethyl acetate with the vegetable oil-based polyols of undecenoic acid modification, and under ice bath, add triethylamine to react 2 hours, then 20-30 DEG C is stirred 24 hours, after suction filtration, obtains product respectively with removing desolventizing after 1% sodium hydrate aqueous solution and distilled water washing, dried over mgso.
2. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, is characterized in that described vegetable oil is one or more mixture of rapeseed oil, corn oil, soybean oil, olive oil, grape-kernel oil, linseed seed oil and tung oil.
3. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, the content that it is characterized in that renewable carbon atom is 100%.
4. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, has branched structure, and the degree of branching is relevant to the number of unsaturated double-bond on vegetable oil raw materials, is 1 ~ 2 times of the contained double key number object of vegetable oil.
5. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, its unsaturated degree of functionality is relevant to the number of unsaturated double-bond on vegetable oil raw materials, is 1 ~ 2 times of the contained double key number object of vegetable oil.
6. according to the pure plant oil based polyenoid class UV-curable prepolymer described in claim 4 or 5, on described vegetable oil raw materials, the number of unsaturated double-bond is 2 ~ 8.
7. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, its molecular weight is 1672 ~ 3868g/mol.
8. pure plant oil based polyenoid class UV-curable prepolymer according to claim 1, described multi-thiol compound is the material containing 2 and above sulfydryl.
9. pure plant oil based polyenoid class UV-curable prepolymer according to claim 8, described multi-thiol compound is 1.6-ethanthiol, pentaerythrite tri-thiol propionic ester or pentaerythrite four mercaptopropionic acid esters.
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| CN105001088B (en) * | 2015-07-27 | 2017-04-19 | 江西科技师范大学 | Method for preparing all-bio-based photocuring activated monomer and application of all-bio-based photocuring activated monomer |
| CN109666303A (en) * | 2019-01-25 | 2019-04-23 | 付远 | A kind of visible light 3D printing technique of epoxidized vegetable oil |
| CN111154071B (en) * | 2019-12-30 | 2021-03-26 | 华南农业大学 | Multifunctional epoxy vegetable oil-based UV curing prepolymer and preparation method and application thereof |
| CN116333314A (en) * | 2023-04-12 | 2023-06-27 | 华南理工大学 | Method for preparing degradable polyester based on solvent-free polymerization of 10-undecylenic acid |
Citations (4)
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| US6433121B1 (en) * | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
| CN1837181A (en) * | 2006-04-16 | 2006-09-27 | 南京红宝丽股份有限公司 | Bio-based polyhydric alcohol prepared by using rape seed oil |
| CN101583651A (en) * | 2006-09-04 | 2009-11-18 | 生物能源株式会社 | Polyester polyol |
| CN101641324A (en) * | 2007-01-12 | 2010-02-03 | 陶氏环球技术公司 | Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433121B1 (en) * | 1998-11-06 | 2002-08-13 | Pittsburg State University | Method of making natural oil-based polyols and polyurethanes therefrom |
| CN1837181A (en) * | 2006-04-16 | 2006-09-27 | 南京红宝丽股份有限公司 | Bio-based polyhydric alcohol prepared by using rape seed oil |
| CN101583651A (en) * | 2006-09-04 | 2009-11-18 | 生物能源株式会社 | Polyester polyol |
| CN101641324A (en) * | 2007-01-12 | 2010-02-03 | 陶氏环球技术公司 | Hydroxyl-terminated or carboxylic acid- terminated reactive monomer compositions, their preparation and their use |
Non-Patent Citations (1)
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| Fatty Acid-Derived Diisocyanate and Biobased Polyurethane Produced from Vegetable Oil: Synthesis, Polymerization, and Characterization;Leila Hojabri et al.;《Biomacromolecules》;20090312;第10卷(第4期);884-891 * |
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Effective date of registration: 20180425 Address after: 512400 Pearl Industrial Park, Nanxiong, Shaoguan, Guangdong Patentee after: Nanxiong USTC Technology Co., Ltd. Address before: 330013 605 Fenglin Road, Nanchang Economic Development Zone, Jiangxi Patentee before: Jiangxi Science & Technology Normal University |
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